Composition and method for treating hay and similar matter

ABSTRACT

A method of preserving agricultural products or materials such as hay and silage is disclosed. The method comprises the utilization of a composition for coating the material in order to form a water-repellent protective coating thereon. Preferably the coating includes a preserving agent, having substantial antimicrobial acitivity. Further, in some instances the coating may include an adhesive forming constituent, enabling outer layers of material to become tightly bound in the stack, bale or pile of material being treated. When the latter adhesive compositions are utilized, the treated material tends to retain its physical integrity, against loose portions becoming detached therefrom. Also disclosed are preferred compositions for achieving the methods of treatment, and also preferred methods for preparing certain of the preferred compositions.

BACKGROUND OF THE INVENTION

The present invention relates to methods of treating agriculturalmaterials and in particular to methods of treating cut or harvested hay,milo and similar materials. The method is particularly adapted to thetreatment of freshly cut hay and to the preservation of hay bales orhaystacks by the application of preferred compositions according to thisdisclosure.

Freshly cut hay is generally processed into bales or stacks for storage.These have been of a variety of sizes, but in the past most hay bales,such as square bales, were usually 2 to 3 cubic feet in size. However,more recently newer baling techniques have led to production of largecircular bales of about 100 cubic feet in size and weighing 1,200 to1,500 pounds. Also, many hay cutting and storing techniques produce verylarge stacks that are much larger than even the largest bales.

Hay bales and/or stacks may be transported over considerable distancesand stored for considerable lengths of time before use. During anytransport or storage both physical and chemical changes can occur in thehay, lessening its value and usability as animal feed.

Physical changes in the hay are more prevalent in large bales and stacksthan in smaller bales. The physical changes are often due to the largeweight of the bales or stacks. The outer and lower layers of these heavyhay bales and haystacks can become loose, causing large amounts of hayto fall from the bale or stack during transportation. The losses areoften between 8 and 30 percent of the bale, and on occasion evengreater. This not only causes inconvenience and financial loss, but insome instances it can be hazardous. For example a transported stack ofhay, when carried over a highway, may drop as much as 30 percent of itsweight onto the road, forming an obstruction.

Another way in which portions of hay material may be lost is due toweather, for example high winds or heavy rains. Also extensive shock orvibration during transport can cause substantial losses from eventightly stacked piles of material.

In the past these physical changes have been less of a problem, due tothe smaller size of the hay bales. Smaller hay bales may be tightlybound with baling wire, and are therefore less likely to undergo theabove-described loss. Thus, until relatively recently, there has beenless need to control this problem.

Chemical changes in the hay, generally deterioration and rot leading tonutritutional losses, occur in part due to moisture in the hay and alsomicrobial action within the bales or stacks. The moisture may enter thehay as a result of rains and the like. Very large hay bales or stacksmay be particularly slow to dry, and be particularly hard to keep dry,especially when frequent exposure to rain occurs.

Microbial action has long been recognized as a source of problems infreshly cut materials, especially hay. Most of the losses due tomicrobial action occur within the first few days or weeks of the balingor stacking. The microbial action produces high temperatures within thebales, leading to the nutritional loss prior to a complete drying of thehay.

In the past different approaches have been taken in attempts to solveeach of the above problems, and no single unified solution has beenachieved. With respect to microbial action, generally anti-microbialmaterials have been added to cut agricultural material. For examplepreservatives have been added to fodder being stored.

With respect to the problem of water due to rains or the like, generallythe haystacks or bales, when sun is not necessary, have been covered bywaterproof or water resistant coverings, such as plastic tarps or thelike, or the material has been stored indoors.

With respect to losses due to loose hay in outer layers of the stacks orbales, past solutions have generally involved the use of baling wire,cord or the like to tie the bale or stack together. Of course with verylarge stacks or bales this can be difficult to manage.

Thus, no satisfactory, unified approach to the problem has yet beendeveloped. The multiplicity of activity required by the approacheslisted above may not only be relatively expensive and inconvenient, butalso may require substantial expenditure of time on the part of farmersduring a period of the growing season in which time is short andvaluable. Further, in some instances the solutions have been less thaneffective. For example, covering hay with a tarp can prevent the sun andair from getting to the hay, leading to ineffective drying. It hasalready been mentioned that for large haystacks and large bales bindingwith baling wire, cord or the like can be ineffective, especially unlesslarge amounts of wire or cord are used.

OBJECTS OF THE INVENTION

Therefore the objects of the present invention are: to provide a methodof preserving cut agricultural products and silage; to provide such amethod especially suited for the preservation of hay; to provide amethod of treatment of a haystack or hay bale to inhibit the retentionof moisture therein; to provide a method of treatment of a haystack orhay bale to inhibit microbial action; to provide a method of treatmentof a haystack or hay bale by application of a chemical composition, toretard the retention of moisture and also to retard microbial action; toprovide such a method which includes treatment of the haystack or haybale with an adhesive to cause outer layers of the haystack or hay baleto become adhered together, reducing loss due to weather, travel or thelike; to provide a chemical composition for application to cutagricultural materials in order to achieve the application of anadhesive to outer portions of the cut material to retain same together,while at the same time treating the harvested material to generate asubstantial tendency to repel water and minimize microbial action; toprovide such a composition especially suited for treatment of haystacksand hay bales; to provide such a composition which is generally readilyacceptable to livestock that are likely to feed on the harvestedmaterial; to provide such a method and composition which may involvetreatment with materials generally regarded as safe for application tofeed materials for livestock involved in the human food cycle; toprovide such a method which is relatively easy to effect; to provide acomposition for use in such a method which is relatively easy tomanufacture and apply; to provide such a composition which is relativelyinexpensive to produce and which can be produced from readily availablematerials; to provide such a composition which is particularly welladapted for the proposed usages thereof; and, to provide such a methodwhich is particularly well adapted for use in a variety of types offarming.

Other objects and advantages of this invention will become apparent fromthe following descriptions wherein are set forth by way of illustrationand example certain embodiments of this invention.

DESCRIPTION OF THE INVENTION

As required, detailed embodiments of the present invention are disclosedherein; however, it is to be understood that the disclosed embodimentsare merely exemplary of the invention, which may be embodied in variousforms. Therefore, specific details disclosed herein are not to beinterpreted as limiting, but rather merely as a basis for the claims andas a representative basis for teaching one skilled in the art tovariously employ the present invention in virtually any appropriatemanner.

The basic methods proposed in this invention call for application, tothe exterior layers of hay bales and stacks, or bales and stacks ofother agricultural materials and products such as common silage, ofcoating materials capable of protecting the physical integrity of thebales and stacks and/or inhibiting unfavorable nutritutional changes dueto moisture and microbial action. The preferred coatings are preparedfrom agents that are generally considered nutritionally andtoxicologically safe for the animals being fed. Thus, many of thecompositions described herein are made with food additives or chemicalsgenerally regarded as safe, that is GRAS materials.

Generally, the coatings are emulsions, mucilages or suspensions preparedso that they may be applied by spraying or other surface application toexterior layers of hay bales or stacks in the field, usually shortlyafter cutting or stacking. While the treatment may occur at a latertime, it is preferable to apply it early, to provide the best protectionfor the hay or other harvested material. In some instances it may bedesirable to install spraying or spreading equipment directly in thecutting and/or baling machinery for application immediately aftercutting or bale formation.

Two basic types of formulations have been developed for application tocut agricultural products, especially hay, according to the presentinvention. The first type of formulation is an emulsion which is appliedto the surface of individual fibers of hay, to generally coat the hay,creating a somewhat water repellent surface coating. Preferably suchcompositions include antimicrobial compounds, or preservatives, toinhibit deterioration of the hay. Thus, when the first type offormulation is applied to the haystack, the outer layers of the haystackbecome generally water repellent and also microbial action is inhibitedwithin the stack.

The second general type of formulation may be generally characterized asan adhesive mucilage. When applied to a haystack or hay bale, the outerlayers of the haystack will become bound together, leading to inhibitionof breaking apart of the hay bale, that is retention of physicalintegrity. Further, generally, the adhesive layer will be somewhat waterrepellent. In addition the preferred adhesive mucilage formulations,according to the present invention, include a preservative orantimicrobial compound to inhibit deterioration and rot.

Adhesive Compositions

Adhesive materials according to the present invention may bemanufactured in two forms. First, they may be made in a somewhat fluidform, for example as a concentrate to be diluted with water prior tospraying on a hay bale. Alternatively, they may be manufactured in asomewhat solid form for storage, the solid to be dissolved in or addedto water, prior to application on cut materials such as a haystack orhay bale.

The preferred adhesive formulations according to the present inventionhave, as their primary active component for adhesive action, casein.Casein is a phospho-protein generally found in milk, beans and nuts.Other adhesive forming compounds might be used, however casein willgenerally be preferred since it is readily available and well toleratedin animal feed and the human food cycle. It is also very effective informing a water-resistant adhesive, under certain circumstances.

Casein is only sparingly soluble in water, and its isoelectric point isaround pH 4.7. For ease of handling and effectiveness in formulationsaccording to the present invention, the casein is treated with a base,to substantially form a caseinate salt, preferably sodium caseinate.Also, the casein is used in the presence of an emulsifier or a group ofemulsifying agents, to encourage formation of an easily handledsuspension, emulsion or solution. Further, a plasticizer may be includedto aid in formation of a desired adhesive.

The preferred base for treating the casein, according to the presentinvention, in part depends upon the nature of the composition beingformed. If a somewhat dry powder or cake is desired, then a preferredbase has been found to be sodium carbonate, Na₂ CO₃. While sodiumbicarbonate might also be useful, in some trials it has been found thatsodium bicarbonate/casein mixtures often form a foam or flock duringmixing, which can delay application or cause difficulty in handling.

On the other hand, if the compounds are being mixed together insolution, the preferred base has been found to be diethanolamine. It isrecognized, however, that for either situation, that is the solid or thefluid form, a variety of bases might be used. Generally, what isrequired is that the pH of the final solution be appropriate for keepingthe casein and other components from precipitating or forming globulesor masses.

It is believed that a variety of emulsifiers or mixtures of emulsifyingagents may be used. In particular, emulsifiers of use with the presentinvention will be those which tend to form oil-in-water emulsions,similar to milk. In this manner the aqueous mixtures of the presentformulations will generally not separate and will be easier to applyeffectively. Also, they can readily be diluted with water forapplication, when necessary.

Several general types or classes of emulsifiers have been identified aspreferred emulsifiers for the present formulation. The first of these ispolyethelene glycol emulsifiers. A well-known and useful such emulsifieris a polyethelene glycol 400 such as that sold under the trade nameCarbowax 400 by Union Carbide. The number "400" generally indicates thegrade of the polymer and is related to its molecular weight. Suchcompounds are waxlike solids which dissolve in water to form transparentsolutions. They generally do not hydrolyze or deteriorate o storage, andthey, generally, do not support mold growth.

An alternate general type of preferred emulsifier or emulsifying agentfor the present invention is a polyacrylamide polymer. Many suchcompounds are known, several known ones being sold under the trade namesCarbopol 934-P (Dow Chemical) and Separan NA-202 (Dow Chemical). Suchcompounds are generally water soluble resins which have very goodsuspending, thickening and gel forming properties. Separan NP-202 is,presently, probably the more preferred of the two compounds for use inthe human food cycle, due to its apparent greater acceptance by the Foodand Drug Administration.

It is also believed that numerous types of plasticizers might be usedwith adhesive mucilages according to the present invention. A preferredplasticizer has been determined to be glyceryl triacetate (triacetin), aknown food additive, plasticizer and solvent.

Another emulsion stabilizer which might be used in formulationsaccording to the present invention is carboxymethylcellulose. Generally,in the compositions used, the carboxymethylcellulose will be in the formof a salt. In most formulations according to the present invention, thepresence of base will generate formation of sodiumcarboxymethylcellulose.

As indicated above preferred formulations according to the presentinvention also include a preservative or preserving agent to inhibitmicrobial action. While these are not required for the preparation of agood adhesive emulsion or mucilage, such a compound will generallyincrease the effectiveness of the composition as a hay preservative. Anumber of agents are well known. However, preferred ones according tothe present invention are propionic acid or propionic acid salts. It hasbeen found that propionic acid itself is generally preferred, as it doesnot appear to inhibit formation of the desired mucilage or emulsion.Alternate preservatives may include such compounds as calciumpropionate, sodium propionate, and potassium sorbate.

Adhesive Formulation 1

The following is a preferred adhesive formulation according to thepresent invention. The percent compositions are by weight, the unlistedcomponent being water.

5-10% casein (edible)

0.5 to 1.0% diethanolamine

0.25 to 0.5% sodium carboxymethylcellulose

0.25 to 0.5% triacetin (glycerol triacetate)

0.5 to 1.5% polyethelene glycol 400 (for example Carbowax 400)

0.1 to 0.4% propionic acid (food grade)

The above formulation is a viscous mucilage, and requires substantialpressure for application. For field use hand pumps or mechanical pumpsmight be used. The coating is to be sprayed or otherwise spread onto theouter surface of the bales or stacks in quantities sufficient to coverthe entire outer surface of the hay, or other material being coated. Thecoating should generally be applied in sufficient amount for penetrationof from one to three inches. Preferably from about 1,500 to 3,000milliliters (ml) of such a coating should be applied for the protectionand stabilization of a bale or stack including about 1,200 to 1,500pounds of material. The amount of coating to be applied varying,proportionally, with concentration and with amount of cut material to becoated.

It has been found that the nature of and order of steps taken in themixing of the components can make a considerable difference in the easewith which the mucilage or adhesive formulation can be formed. Ifappropriate care is not taken, separation of the mixtures may occur, orsome components may settle or agglomerate. The following examples reportpreferred preparations of adhesive formulations generally according toFormulation 1 given above. In several instances some modifications incomponents were made, these are mentioned where appropriate.

EXPERIMENT 1

A first solution (Solution A) was prepared including 36 grams (gm) ofcasein slurried in about 197 ml of deionized H₂ O at about 60 degreescentigrade (°C). To this slurry was added about 3.0 ml ofdiethanolamine, with continuous stirring at about 60° C. The pH of thismixture was about 7.2 to 7.3, and the mixture was allowed to stand forabout 30 minutes at 60° C.

A second solution (Solution B) was prepared from the addition of about1.0 gm of sodium carboxymethylcellulose to 195 ml of deionized H₂ O, atroom temperature. To this mixture was added about 2.0 ml of triacetinand about 2.0 ml of Carbowax 400, slowly and with stirring. Thisresulted in the formation of a thick, nearly water-clear, viscoussolution having a pH of approximately 7.2.

Solution B was added to Solution A with constant stirring, to yield aviscous mucilage. To this was added, very slowly, about 1.2 ml ofpropionic acid, to yield a solution having a final pH of about 6.2 to6.3. It was found that the propionic acid addition must be done veryslowly, otherwise sometimes the solution will cease to maintain an evenconsistency, as for example by formation of globules or masses therein.

Immediately upon formation, the above mucilage was observed to have somefoam formed therein, which tended to break after standing for about onehour. The final concentrations, by weight, of the components used informing the mixture, other than water, were as follows:

About 9.0% casein

About 0.75% diethanolamine

About 0.5% triacetin

About 0.5% Carbowax 400 (a polyethelene glycol compound);

About 0.3% propionic acid; and

About 0.25% sodium carboxymethylcellulose.

The above composition was tested by application to test hay bales. Thetest hay bales used were approximately 4 inches by 15 inches by 20inches. Each of two bales was treated with about 75 ml of theabove-referenced mucilage by pouring the mucilage onto the bale, andspreading it thereover. By about one hour after application the baleswere essentially dry and the outermost hay fibers were very tightlyadhered to one another. The test bales were exposed to water sprayingfor about 11/2 hours, an equivalent to about a 1.0 to 1.5 inch rain.Within about several hours the bales had dried and were resprayed withwater for another 1.5 hours, again approximating a 1.0 to 1.5 inchrainstorm. After the bales had dried they were examined. The outerportions of the bales were very tightly adhered, and no loose fiberswere observed to fall off of the bales.

The above-treated bales were placed in a feeding trough for cattle.Almost immediately after the bales were placed in the feeding trough,several cattle ate the majority of the treated and also control bales.There did not appear to be any preference for the cattle between treatedand untreated bales, and the treated bales were entirely consumed.

EXPERIMENT 2

A first solution (Solution C) was made by mixing 40.0 gm of casein andapproximately 197 ml of deionized H₂ O, at 50° to 60° C., to form aslurry. To this was added about 3.0 ml of diethanolamine, to dissolvethe casein and form the mucilage. The pH of this mucilage was about 6.8to 7.0.

A second solution (Solution D) was formed by mixing approximately 1 gmof sodium carboxymethylcellulose with 196 ml of deionized H₂ O, at roomtemperature, to form a solution. To this was added about 2.0 ml oftriacetin and about 2.0 ml of Carbowax 400.

Solution D was added to Solution C with continuous stirring, to form anoverall mixture having a pH of approximately 7.0. The total volume ofthe mixture was about 400 ml.

150 ml of the above mixture of solutions C and D was separated and tothis was added approximately 0.45 ml of propionic acid. The addition wasfairly rapid and resulted in the formation of some clabber, that iswhite globs of clotted material. The clabber slowly went intosuspension, upon shaking by hand. The pH of the final mixture was testedto be approximately 6.0.

The composition of the final solution, by weight, was as follows:

About 10% casein;

About 0.75% diethanolamine;

About 0.25% sodium carboxymethylcellulose;

About 0.5% triacetin (glyceryl triacetate);

About 0.5% Carbowax 400; and

About 0.3% propionic acid.

The above formulation was tested on a bale of hay having dimensions ofabout 4"×15"×20". The bale was treated with about 75 to 100 ml of themixture, by spreading or pouring thereon, to completely cover the bale.The bale was allowed to dry at a temperature of about 85 to 90 degreesfahrenheit (°F.). After about 1 hour the bale was found to beessentially dry and brittle, with the outer layers of hay substantiallyadhered thereto.

The bale was set outside and exposed to heavy dews on each of fournights. The bale was then exposed to heavy lawn spray for about 1.5hours, approximating about a 1.0 to 1.5 inch rainfall. A second exposureto heavy spraying, roughly equivalent to a 1.0 to 1.5 inch rainfall wasmade. The bale was then allowed to dry.

The bale was found to have those hay fibers in the outer 1.0-1.5 inchestightly adhered to one another. The inside fibers of the bale were verygreen compared to the outer bale fibers and also a control, untreatedbale. The outer fibers were found to be well coated, as well as adhered,by the polymer coating.

EXPERIMENT 3

A variation in Formulation 1 was made utilizing calcium propionate,rather than propionic acid, as the preservative or preserving agent. Thecomposition was made as follows:

A first solution (Solution E) was made from mixing 32 gm of casein and197 ml of deionized H₂ O, at 50° to 60° C., to form a slurry. To thiswas added about 3.0 ml of diethanolamine, with continuous stirring, toyield a yellow-gray heavy mucilage. It is noted that the volume of thesolution swelled considerably during addition of the diethanolamine. Thefinal solution had a pH of about 7.5.

A second solution (Solution F) was made by mixing about 1.0 gm of sodiumcarboxymethylcellulose with about 197 ml of deionized H₂ O, at roomtemperature. To this was added about 2.0 ml of triacetin; about 2.0 mlof Carbowax 400; and about 1.2 gm of calcium propionate. This yielded amixture which was slightly opaque and had a pH of approximately 6.5.

Solution F was added to Solution E with continuous stirring, to form ayellow-gray mucilage having a pH of about 8.0. The mucilage was verythick and had a total volume of about 400 ml.

The final composition of this mixture, by weight, was as follows (theremaining component being primarily water):

About 8.0% casein;

About 0.75% diethanolamine;

About 0.25% sodium carboxymethylcellulose;

About 0.5% triacetin (glyceryl triacetate);

About 0.5% Carbowax 400; and

About 0.3% calcium propionate.

An experimental hay bale having dimensions of about 4"×15"×20" wastreated with about 75 to 100 ml of the above-referenced mixture and wasplaced outdoors to be dried. After drying the bale was exposed to aheavy spray for approximately 1.5 hours, to approximate a 1.5" rainfall.The bale was allowed to stand overnight to dry, and then was againsprayed with water for about 1.5 hours to approximate a second 1.5 inchrainfall. Several days later the bale was exposed to light intermittentrainfall over a number of hours, totaling approximately 1.5". Also, overseveral more days the bale was exposed to heavy mist and dew. Finally,the bale was exposed to a 2.5 inch rainfall over a couple of hours. Thebale was then examined.

The bale was observed to have its outer layers, for approximately 1.0inch deep, tightly adhered and brittle, however the adhered fibers couldbe pulled apart from one another by hand. Individual fibers wereobserved to be well coated with the compound.

EXPERIMENT 4

Another variation in a Formulation 1 mixture, this time utilizing sodiumpropionate as the preservative, was tested. The composition was preparedas follows:

A first solution (Solution G) was prepared by mixing approximately 18 gmof casein with about 98.5 ml of deionized water, at approximately 60°C., to form a slurry. The slurry was allowed to stand, at 60° C., forabout 20 minutes. To this was added about 1.5 ml of diethanolamine, withconstant stirring, at still about 60° C.

A second solution (Solution H) was prepared by mixing approximately 0.5gm of sodium carboxymethylcellulose with about 98.0 ml of deionized H₂O, to form a slurry. To this was added about 1.0 ml of triacetin, withstirring, and about 1.0 ml of Carbowax 400, with stirring.

Solution H was added to Solution G with continuous stirring, forming anoverall mixture having a pH of about 8.0. To this was added about 0.6grams of sodium propionate, slowly and with continuous stirring. Thefinal mixture was a heavy mucilage having a pH of approximately 8.0 andthe following composition of added ingredients, by weight, the remainderbeing primarily water:

About 9.0% casein;

About 0.75% diethanolamine;

About 0.25% sodium carboxymethylcellulose;

About 0.5% triacetin (glyceryl triacetate);

About 0.5% Carbowax 400; and

About 0.3% sodium propionate.

The above mixture was tested on two hay bales each having measurementsof about 4"×15"×20". About 75 ml of the mixture were added to each baleand spread thereover. The bales were allowed to dry, over a time periodof about one to two hours. The bales were then exposed to outdoorweather conditions, on a September day having a high of about 60° F. anda low during the night of about 35° to 40° F. The next day the baleswere sprayed for about 1.0-1.5 hours with water, to approximate a1.0-1.5 inch rainfall. The bales were allowed to dry overnight and werethen again exposed to a 1.5 hour spraying, approximating a second1.0-1.5 inch rainfall. Over the following two days the bales wereexposed to heavy, but intermittent, rainfall amounting to approximately2.4 inches. The bales were then allowed to dry for several days, beingexposed to intermittent, gentle rains. Approximately 12 days later thebales were exposed to a very heavy rainfall of about five inches, andthen were exposed to a lighter rainfall, over several more days, ofabout 0.5 to 1.0 inch. The bales were then examined.

Each bale was observed to have an outer layer of fibers which were welladhered to the bale but which could be pulled apart manually.Substantially all outer fibers of the bales were observed to be brittleand coated with material. A slight amount of moisture was found in theinner portion of the bales, and the bales were somewhat greener than acontrolled, untreated, bale that had been exposed to the same testing.

ALTERNATE ADHESIVE MUCILAGE: FORMULATION 2

As indicated above, alternate formulations using: different emulsifyingagents and thickening agents; and propionic acid salts or similarantibacterial agents, are possible according to the present invention. Aparticularly good alternative to Formulation 1-type mixtures is asfollows, the composition being given by weight and the remainder beingprimarily water:

About 6 to 10% casein (edible);

About 0.5 to 1.2% diethanolamine;

About 0.052 to 0.2% of a polyacrylamide emulsifying agent (for exampleCarbopol 934-P);

About 0.2 to 0.4% propionic acid (food grade).

Generally Formulation 2 compositions should be used similarly toFormulation 1 compositions, that is by the addition of approximately1,500 to 3,000 ml of coating for the protection and stabilization ofabout 1,200 to 1,500 pound stacks or bales of hay. The amount ofsolution should be modified, proportionately, for different sizedhaystacks or bales, and different concentrations of mixtures. It isnoted that other polyacrylamide emulsifiers, such as Separan NP-202 maybe substituted for Carbopol 934-P. Generally, a sufficient amount ofemulsifier should be added to yield the desired consistency, with theabove suggested concentration being preferred for Carbopol 934-P.

Again, it is believed that the order and method of mixing of thecomponents are important in yielding a mucilage that is free flowing andrelatively free from any clotted matter or separation. The followingexperiments exemplify preparation and use of Formulation 2 typecompositions.

EXPERIMENT 5

A composition of material according to Formulation 2 was prepared asfollows:

About 36 gm of casein was added to about 396 ml of deionized H₂ O atabout 60° C., with constant stirring. A slurry was formed which wasallowed to sit for several minutes.

About 3.0 ml of diethanolamine were added to the slurry, with constantstirring, again at about 60° C. The resulting mixture had a pH of about7.6 to 7.8 and was allowed to stand for about 30 minutes.

About 0.4 gm of Carbopol 934-P were added to the casein mixture, veryslowly, resulting in a mixture having a pH of about 7.4 to 7.5. To thiswas slowly added about 1.2 ml of propionic acid, giving a resultingmixture having a pH of about 6.0 to 6.2.

The resulting mixture had a total volume of about 400 ml and was a verythick, uniform, yellow-gray mucilage that was mobile, that is, it wouldflow. The final mixture had the following approximate composition, byweight (the remaining component being primarily water):

About 9.0% casein;

About 0.75% diethanolamine;

About 0.1% Carbopol 934-P; and

About 0.3% propionic acid.

The above formulation was tested on two hay bales each having dimensionsof about 4"×15"×20". Each bale was treated with about 75 ml of themucilage, which was added by pouring over the bale and spreadingthereon.

After about one hour the bales were observed to be dry, and the outerfibers were noted to be very tightly adhered to the bales. The baleswere exposed to a spraying of water, for about 1.5 hours, approximatingabout 1.5" of rainfall. The bales were then allowed to dry for severalhours and were resprayed for another 1.5 hours, again approximating a1.0-1.5 inch rainfall. The bales were then allowed to stand for severaldays.

Upon examination both bales were found to have the outer fibers verytightly adhered to the bale, with very few loose fibers being observed.The two bales were then placed in a feed trough for cattle, along withother bales of hay. The cattle immediately ate most of the bales, withno apparent preference over control, untreated, bales.

EXPERIMENT 6

An adhesive mucilage composition according to Formulation 2 was preparedas follows:

About 16 gm of casein were mixed with 197 ml of deionized H₂ O, atapproximately 60° C., to form a slurry. To the slurry was added about2.0 ml of diethanolamine, slowly, with continuous stirring. This mixturewas allowed to stand for about 30 minutes and was observed to have a pHof about 8.5.

About 0.2 gm of Carbopol 934-P were very slowly added to the abovemixture, to form an off-white, thick, mucilage. The pH of this resultingmucilage was about 8.2 to 8.3.

Next about 0.6 ml propionic acid were added very slowly to the mixture.The resulting mixture was a very thick heavy mucilage that was mobile.The pH of the mucilage was observed to be about 7.8 to about 8.0. Somefoam was observed, which disappeared upon standing.

By weight, the composition of this formulation, in terms of addedcomponents, was as follows (the remainder being primarily H₂ O):

About 8.0% casein;

About 1.0% diethanolamine;

About 0.1% Carbopol 934-P; and

About 0.3% propionic acid.

Two test bales, each having a dimension of about 4"×15"×20", were eachtreated with about 75 ml of the above mixture. The bales were allowed tostand and dry overnight. They were then sprayed with water from a hosefor about 1.5 hours, approximating a 1.0-1.5 inch rainfall. The baleswere again allowed to dry overnight, and then were exposed to a 1 inchrainfall over several hours.

Upon final evaluation the hay bales were observed to be well coated onall of the outer fibers, with the outer fibers being fairly well adheredto the bale. The insides of the bales were observed to be relativelydry.

EXPERIMENT 7

A modification in a Formulation 2 type adhesive mucilage was prepared asfollows:

About 18 gm of casein were mixed with about 198.5 ml of deionized H₂ Oat about 60° C. To the resulting slurry about 1.5 ml of diethanolaminewere added, with constant stirring. The pH of the resulting mixture wasabout 8.2 to 8.3.

To the above mixture were added about 0.2 grams of Carbopol 934-P, withconstant stirring, to form a slurry having a pH of about 8.0.

To the resulting mixture was added about 0.6 gm of sodium propionate,very slowly with constant stirring. The resulting mucilage had a pH ofabout 7.5 to 7.6, was observed to be apparently uniform in consistencyand was very heavy, but mobile. The resulting mixture had been formedfrom the following components, by weight (the remaining constituentbeing water):

About 9.0% casein;

About 0.75% diethanolamine;

About 0.1% Carbopol 934-P; and

About 0.3% sodium propionate.

The above composition was tested on two hay bales each having dimensionsof about 4"×15"×20". Each bale was treated with about 75 ml of thecomposition, by pouring the composition thereon and spreading thereover.The bales were observed to be dry after about one to two hours. Theywere then allowed to stand overnight.

Both of the bales were sprayed with water for about 1.5 hours,approximating a 1.0-1.5 inch rainfall. They were then allowed to standovernight and were again sprayed for about 1.5 hours, to approximate asecond 1.0-1.5 inch rainfall. The bales were again allowed to standovernight.

Over the next two days, the bales were exposed to a heavy, butintermittent, rainfall totaling about 2.4 inches of rain. The bales werethen allowed to stand for about three days, and on the fourth day theywere exposed to about a 0.6 inch rainfall. The bales were allowed tostand about five more days, after which they were exposed to about a 4.7inch rainfall, that was very heavy and which occurred over a period ofabout two days. The bales were then allowed to stand for several moredays, and were exposed to about 0.7 inches of a light, intermittent,rainfall. The bales were then examined.

The bales were both observed to have their outer fibers fairly welladhered to the bale, and difficult to separate. The hay fibers wereobserved to be brittle and well coated with the adhesive. Insideportions of the bales were fairly dry and green, relative to anuntreated but similarly exposed control.

ALTERNATE ADHESIVE: FORMULATION 3 FOR DRY MIX COMPOSITIONS

Under certain circumstances it may be desirable to have the adhesiveformulation available in a dry mix form. That is, the aboveformulations, Formulations 1 and 2, are generally heavy, viscous butfluid, mucilages. It is foreseen that a dry mix, to be diluted withwater for use, would be, in many instances, easier to handle and store.Generally, preferred components of such a dry mix are as follows:

casein;

sodium carbonate;

a polyacrylamide polymeric emulsifier (for example Carbopol 934-P orSeparan NP-202); and

potassium sorbate (food grade).

It is noted that some substitutions may be made, for example, it isforeseen that sodium propionate might be substituted for potassiumsorbate as the preservative.

Preferably, the dry mix is prepared in such a manner that when mixedwith water, the resulting hay treatment composition will have thefollowing composition of constituents, by weight (the remainder beingsubstantially water):

About 4 to 10% casein;

About 1 to 3% sodium carbonate monohydrate;

About 0.1 to about 0.4% potassium sorbate; and

About 0.05 to 0.3% polyacrylamide polymer (Carbopol 934-P or SeparanNP-202, for example).

A preferred dry mix powder for yielding the above hay treatment includesthe following components, by weight:

About 78.74% casein (food grade);

About 18.2% sodium carbonate monohydrate;

About 2.62% potassium sorbate (food grade); and

About 0.44% polyacrylamide polymer (for example Carbopol 934-P orSeparan NP-202).

It is noted that anhydrous sodium carbonate could readily be substitutedfor the monohydrate.

During the mixing with water, part or all of the casein is converted tosodium caseinate and, if acidic, the polyacrylamide polymer is convertedto its sodium salt. The resulting spray is preferably used in quantitiesof about 1,500 to 3,000 ml of spray per 1,200 to 1,500 pounds of hay,with the amount of spray being varied, proportionately, with the amountof hay.

A particular problem with developing a dry mix has been that the mixmust be such that it can be readily mixed with water, by the farmer andpreferably by hand, to form a stable mucilage. In some instances it willbe preferred to use hot tap water, in order to lessen the length of timetaken for mixing.

The following Experiments relate to adhesive formulation, generallyaccording to Formulation 3 type compositions.

EXPERIMENT 8

A composition generally according to Formulation 3 was prepared asfollows:

The following dry ingredients were molded together:

18 grams of casein;

1 3.5 grams of Na₂ CO₃ (anhydrous);

0.1 grams of Carbopol 934-P; and

0.6 grams of potassium sorbate.

It is noted that anhydrous sodium carbonate was used, however, thehydrous form could have been used just as readily, preferably withaccounting for the weight of water.

The dry mixture was prepared for application to hay as follows:

200 ml of room temperature tap water were added to the dry ingredients,with hand stirring and shaking. It took approximately one hour forcomplete reaction, to form a yellow, very heavy but quite mobile,mucilage, having a pH of about 9.2. The final composition of thesolution, by weight, was as follows (the remaining ingredient being tapwater):

About 9% casein;

About 1.75% Na₂ CO₃ ;

About 0.05% Carbopol 934-P; and

About 0.3% potassium sorbate.

The mucilage was tested as follows:

Two hay bales were prepared each having dimensions of about 4"×15"×20".Each bale was treated with about 50 to 75 ml of the above mucilage, bypouring and spreading the mucilage over the entire outside of the bales.The bales were allowed to dry at a temperature of about 50 to 60 degreesfahrenheit. A 1.5 hour drying period was used.

Shortly after drying, the bales were exposed to about 0.7 inches oflight intermittent rain. Several days later the bales were exposed to afairly heavy frost, and then they were exposed to a spray of waterapproximating a 1.5 inch rainfall. On the next day the bales wereexposed to a further 0.6 inch light intermittent rain, leading to atotal exposure of the bales being about 2.8 inches of rain orequivalent.

The bales were examined, each was substantially identical to the other.A very good adhesiveness in the hay fibers was noticed on the outerportions of the bales, extending to about 1.0 inch inwardly. The insidefibers of the bales appeared green. The adhesion was very tight, and thefibers were nearly impossible to separate from one another, as bypulling.

The treated hay bales were fed to cattle and no problems were observed.

EXPERIMENT 9

A powdered composition was prepared by mixing the following together:

360.0 grams of casein;

70.0 grams of Na₂ CO₃ (anhydrous);

12.0 grams of potassium sorbate; and

2.0 grams of Carbopol 934-P.

The powders were molded together in a plastic container. The dry powdermix was prepared for application as follows:

Approximately 111 grams of the dry powder mix was placed in a one-halfgallon plastic container and about 1,000 ml of room temperature tapwater were added. The mixture was stirred for approximately 3 hours tocompletely suspend the powder.

The adhesive composition was tested as follows:

A plate of glass was covered with plastic and sufficient milo was piledon it to form a pile approximately 8"×12" by 1.5-2" in height.Generally, the pile peaked in the center and sloped toward the edges,with the approximate volume of milo being 90 to 100 cubic inches.

Approximately 100 to 125 ml of the adhesive solution was poured onto themilo pile. The milo was allowed to dry at room temperature overnight.

Some excess mucilage was observed to have moved to the edges of themilo. The pile of milo was observed to be stiff and it appeared to becompletely bound, that is no substantial loose milo was observed.

The treated milo was placed outdoors and within one hour birds had eatenmost of the milo. Thus, the treated milo was not rejected as feed, atleast for birds.

Another test was made, with precautions taken to avoid eating of themilo by birds.

A stack of milo of approximately 8"×12"×1.5" in the center was placed ona plastic covered glass plate. The pile was sprayed with sufficientadhesive solution to appear completely covered. The milo was allowed todry.

The stack of milo was sprayed for about 1.0-1.5 hours with water,creating an equivalent to about 1 inch of rainfall. The pile was allowedto dry overnight, at about 60° to 65° F.

The treated milo pile was observed to still have an adhesive coating,and was fairly rigid, that is fairly free from loose milo material.

The milo stack was again sprayed for one hour with sufficient water toapproximate about 1.0 inch of rainfall, and was again allowed to dry atabout 60° to 75° F., overnight. The milo pile was then exposed to asporadic light rain totaling approximately 0.1 inches, followed by aheavy frost. The stack of milo was observed to be still substantiallycoated with adhesive. The milo was relatively difficult to separate,when compared to non-coated milo that had been exposed to the sameconditions. The coated milo was somewhat darker in color than uncoatedcontrol milo.

EXPERIMENT 10

Sodium caseinate is a commercially available material. The followingexperiment was run to show that sodium caseinate could be substitutedfor casein in the dry mixture.

The following dry mixture was formed:

18.0 grams of sodium caseinate;

About 2.0 grams of sodium carbonate;

About 0.6 grams of potassium sorbate; and

About 0.1 grams of Carbopol 934-P.

It is noted that if no base, such as sodium carbonate, is used the drymix will not dissolve well, that is, it tends to curdle.

An adhesive solution was made by the addition of 200 ml of roomtemperature tap water to the dry powder, with stirring and shaking.Initially some curds formed. However eventually there was substantiallycomplete solubilization of the sodium caseinate, to form a highlyviscous but mobile, opaque, mucilage, having a slight yellow color. ThepH of the mucilage was observed to be about 9.5.

EXPERIMENT 11

The preserving agent or preservative utilized in the adhesive mucilagemay be varied. For example sodium propionate may be substituted for thepotassium sorbate. In order to demonstrate this the instant experimentwas conducted.

A dry mix was made from the following components:

About 9.0 gm casein;

About 2.0 gm Na₂ CO₃ ;

About 0.3 gm sodium propionate; and

About 0.1 gm Carbopol 934-P.

The entire dry mix was added to about 100 ml of room temperature tapwater, by slowly slurrying in the powder with the mixture. The resultwas a fluffy white mucilage having a volume of about 350 ml due tofoaming. The pH of the mucilage was observed to be about 8.5 to 9.0. Itis noted that the rate of mixture with water can be increasedsubstantially by using warm or hot tap water. Upon standing, themucilage eventually separated from the foam, yielding a fairly mobilecompound having the following composition, by weight (the remainingconstituent being tap water):

About 9.0% casein;

About 2.0% sodium carbonate;

About 0.1% Carbopol 934-P; and

About 0.3% sodium propionate.

The above adhesive solution was tested as follows:

Two hay bales having dimensions of approximately 4"×15"×20" were eachtreated with about 50 to 75 ml of the above adhesive solution, bypouring and spreading the mucilage onto and completely over each bale.The bales were placed outdoors to dry at about 50° F. The bales wereobserved to be dry after about 1.5-2.0 hours.

The bales were exposed to heavy, but intermittent, rain, with outdoortemperatures of between 40° and 45° F. The total amount of rain wasabout 2.4 inches over several days. The bales were also exposed to arather heavy frost, after the period of rain.

After several days the bales were exposed to about 0.6 inches more ofrain. Approximately a half week later the bales were exposed to about4.7 inches of rain, which was often very heavy. Several days followingthe last heavy rain, the bales were exposed to two periods of lightrain, each of which totaled about 0.7 inches.

One of the bales was opened and examined. A good adhesive layer of boundtogether hay fibers was observed in about the outer 1.0 inch layer ofthe bale. The inside of the bale wa relatively dry and had a green haycolor, when compared to an uncoated control. Substantial pulling wasnecessary to get the bale to break apart.

EXPERIMENT 12

To demonstrate that an effective, less concentrated, adhesive mucilagecan be prepared, the instant experiment was conducted. The generalpurpose was to show that a less heavy, and more fluid, mucilagecomposition is usable. It is noted that such a solution, while easier tospread, may need to be used in higher amounts on hay to be treated.

The following dry mix was prepared:

About 18.0 grams casein;

About 4.0 grams sodium carbonate (anhydrous);

About 0.6 grams sodium propionate; and

About 0.2 grams of Carbopol 934-P.

The above components were molded into a uniform dry mix. The powder wasdissolved in about 400 ml of room temperature tap water. This was doneby first adding about 200 ml of water to slurry the dry mix, with handstirring. Then an additional 200 ml of water was added to dilute themixture. It is noted that the Carbopol 934-P was the last material to gointo the solution, but eventually it all dissolved with a total solutiontime being about one hour.

The resulting solution was observed to have a pH of about 9.2 to 9.3. Itwas a very mobile but fairly thick mucilage having a slightly yellowcolor. The composition of starting materials in the solution, by weight,was as follows (the remaining constituent being substantially water):

About 4.5% casein;

About 1.0% sodium carbonate;

About 0.15% sodium propionate; and

About 0.05% Carbopol 934-P.

A test hay bale having dimensions of about 4"×15"×20" was prepared andtreated with 150 ml of the above solution. The treatment was by pouringand spreading over the surface of the bale. The bale was allowed to dryat about 45° to 50° F.

The bale was then exposed to about 4.7 inches of rainfall over a two dayperiod, often the rainfall being very hard. On several days followingthe heavy rains, the bale was exposed to a total of about 1.4 inches ofrain and finally a heavy frost.

Upon evaluation the bale showed a very good adhesiveness with nearly allouter fibers of the bale being very tightly adhered, some of the fibersbeing very difficult to separate from the bale. The inside portion ofthe bale was found to be dry and to possess a green hay color.

EXPERIMENT 13

As indicated above, at least one base that might be substituted forsodium carbonate in forming the dry mix is sodium bicarbonate. Anexperiment demonstrating this was conducted as follows:

A dry mix having the following composition was prepared:

About 18.0 grams casein;

About 5.0 grams sodium bicarbonate (anhydrous);

About 0.6 grams sodium propionate; and

About 0.2 grams Carbopol 934-P.

The above dry mix was dissolved in about 200 ml of room temperature tapwater, with hand shaking. There was considerable gas (carbon dioxide)evolution and about 2.5 hours were required to bring about solution andpreparation of the mucilage. The mucilage prepared was found to have apH of about 7.0 to 7.1. It was thick but mobile and had a slightlyyellow color. The composition of starting materials in the mixture, byweight, was as follows (the remaining constituent being primarilywater):

About 9.0% casein;

About 2.5% sodium bicarbonate;

About 0.3% sodium propionate; and

About 0.1% Carbopol 934-P.

The above-referenced solution was tested as follows:

Two hay bales having dimensions of about 4"×15"×20" were prepared. Eachwas treated with about 50 to 75 ml of the above adhesive, by pouring andspreading of the mucilage over the bale. The bales were then allowed todry and were exposed, over about a five day period, to rain or hosespray totaling to an equivalent of about 3.5 inches of rainfall.Further, a fairly heavy frost occurred during the test period.

The hay bales were examined and were observed to have a very goodadhesiveness in the outer fibers; nearly all of the outer fibers beingvery difficult to separate from the bale. The inside of the balesexhibited a green hay color. It was observed that most of theadhesiveness was in about the outer 1.0 inch of the hay bales.

EMULSION COATINGS FORMULATION 4 COMPOSITIONS

It is foreseen that in some instances it may be desirable to utilizevery good coating for the outer fibers of the hay bale, without thetight adhesiveness provided by the Formulation 1, 2 and 3 typecompositions. These compositions might be used, for example, where it isnot believed that the haystack or hay bale will be subject to thosephysical stresses likely to cause breaking apart of the hay, or furtherthey might be used where it is intended that the hay break apartreadily, but where it is also desired that for a period of time outerportions of the haystack or hay bale still be kept coated with asomewhat moisture resistant and antimicrobial coating.

For commercial purposes, generally such an emulsion coating wouldpreferably be prepared in a concentrated form, to be diluted beforespraying onto a haystack or hay bale. Such coatings are generallysubstantially less viscous than adhesive coatings, and therefore couldbe more easily sprayed upon haystacks or hay bales, especially utilizingconventional spraying equipment. Thus, another reason why such coatingsmight be preferred would be due to the ease with which they can besprayed upon hay or other materials.

Generally, emulsion coatings according to the present invention includeat least the following types of constituents:

A principal component is an edible oil, which will help form the waterresistant coating over the harvested material, in particular the haybale fibers. Peanut oil and/or soybean oil will be generally preferred,since they are both readily available, edible and can be used to formeffective coatings. Of the two, soybean oil is preferred.

In such a coating numerous emulsifiers and mixtures of emulsifyingagents may be used to assist in maintaining a mixture of evenconsistency that can be readily sprayed. Also, such compounds will helpin setting up the desired coating. In defining the present invention itwas found that a mixture of the following types of compounds appeared toyield a preferred composition, over the use of the compoundsindividually. The preferred emulsifying agents included: acetylatedmonoglycerides, for example the acetylated monoglyceride compositiongenerally sold under the trade name Myvacet 9-45 (Eastman Chemical);polyethelene glycol-8-oleate compositions such as those sold under thetrade name Witconol H31A (Witco Chemical Co.); and polyacrylamidecompositions such as those generally sold under the trade names Carbopol934-P and Separan NP-202 (Dow Chemical).

Other preferred constituents for such emulsion coatings include apreservative, such as propionic acid, a propionic acid salt, or asimilar type of preservative; a plasticizer/solvent such as glyceryltriacetate (triacetin); and a base such as diethanolamine.

The following is a preferred composition, by weight, for an emulsioncoating to be used on freshly harvested materials such as hay bales andhaystacks. The formulation is for a concentrate, which generally wouldbe diluted with about four volumes of tap water before fieldapplication. The constituent not listed is water. The generalFormulation 4 (concentrate) composition is as follows:

About 16 to 20% soybean oil (edible);

About 16 to 20% Myvacet 9-45 (acetylated monoglycerides);

About 1.0 to 1.5% diethanolamine;

About 1.0 to 1.5% Witconol H31A (polyethylene glycol-8-oleate compounds)

About 1.0 to 2.0% triacetin (glyceryl triacetate);

About 0.25 to 1.0% Carbopol 934-P (polyacrylamide resin); and

About 0.5 to 2.00% propionic acid (food grade).

As with Formulation 1, Formulation 2 and Formulation 3 compounds,generally Formulation 4 compounds, once appropriately diluted, should beapplied in a volume of about 1,500 to 3,000 ml of coating per 1,200 to1,500 pounds of hay, with the amount of coating to be used changingproportionally with the amount of hay to be sprayed. Due to their lessviscous nature, Formulation 4 type coatings may be readily sprayed withordinary paint spraying equipment or similar equipment, when used in thedilution appropriate for field application.

It is noted that in preparing emulsions of numerous components,especially those listed above, the temperature of mixing, the order ofmixing components, the pH of the solution and other, similar, factorsmay be very important in preventing precipitation or formation ofmultiple layers, and in preventing clabber or globule formation andsimilar problems. The following experiments show preferred methods:

EXPERIMENT 14

A first solution (Solution I) was made by mixing about 3.0 ml ofdiethanolamine and about 166.5 ml of deionized H₂ O.

A second solution (Solution J) was prepared by mixing about 60 ml ofsoybean oil with about 60 ml of Myvacet 9-45.

Solution J was added to Solution I with constant stirring. To this wasadded about 4.5 ml of Witconol H31A, with constant stirring. Next about6.0 ml of triacetin were added, also with constant stirring. Theresulting solution was a very fluid, off-white, emulsion.

To this solution was added about 1.2 grams of Carbopol 934-P, veryslowly, to give a thick, almost immobile, off-white emulsion having a pHof about 7.5.

To the above mixture was added, very slowly, about 4.5 ml of propionicacid. The propionic acid tended to reduce the viscosity of the solutionand made the emulsion fairly mobile. The resulting emulsion was veryuniform, off-white in color and had an observed pH of about 6.2 to 6.3.The above concentrated solution could be poured slowly, but relativelyeasily. The final concentration of starting materials of thisconcentrate was as follows:

About 20% soybean oil;

About 20% Myvacet 9-45;

About 1.0% diethanolamine;

About 1.5% Witconol H31A;

About 2.0% triacetin;

About 1.5% propionic acid; and

About 0.4% Carbopol 934-P.

The above concentrate was tested as a coating for hay as follows:

About 50 ml of the concentrate was diluted with about 200 ml of tapwater, to yield a very mobile white emulsion. The emulsion was tested ontwo test bales each having dimensions of about 4"×15"×20". The baleswere treated by spreading and pouring about 75 to 100 ml of the dilutedsolution thereover.

After about one hour the bales were very nearly dry and had a somewhatshiny/waxy look. The bales were exposed to a water spray for about 1.5hours, to approximate a 1.0-1.5 inch rainfall. The bales were allowedseveral hours to dry and were again sprayed for about 1.5 hours,approximating a second 1.0 to 1.5 inch rainfall.

The hay bales were observed to have their external, and many of theinternal, fibers well coated with a brown, waxy and shiny coat. Some,but very little, adhesion was noted among the outer fibers.

The bales were placed in a feeding trough for cattle. No discriminationon the part of the cattle between the treated bales and non-treatedcontrols was observed.

EXPERIMENT 15

A somewhat diluted emulsion coating was prepared to show that peanut oilcan be substituted, at least in some instances, for soybean oil. Thesolution was prepared as follows:

A first solution (Solution K) was prepared from 175 ml of deionized H₂ Oand about 1.0 ml of diethanolamine.

A second solution (Solution L) was prepared from about 10 ml of peanutoil and about 10 ml of Myvacet 9-45.

Solution K was added to Solution L, with constant stirring, in a mixer.The result was a fairly good oil-in-water emulsion having a pH of about10.0. Some tendency of the emulsion to separate, with time, was noted.

About 1.0 ml of Witconol H31A was added to the solution, with stirring.The result was a good oil-in-water emulsion having a pH of about 9.0.

To the above solution was added about 0.4 gm of Carbopol 934-P. TheCarbopol was added slowly by powdering into rapidly stirred emulsion.The result was a very thick, but somewhat stable, mobile, white,oil-in-water emulsion having a pH of about 8.0.

The composition of starting materials in the above mixture, by weight,was as follows (the remaining constituent being water):

About 5.0% peanut oil;

About 5.0% Myvacet 9-45;

About 0.5% Witconol H31A;

About 0.2% Carbopol 934-P; and

About 0.5% diethanolamine.

The above solution shall be referred to, in the following description asSolution M.

A fourth solution, Solution N was prepared from about 99 ml of deionizedH₂ O and about 1 ml of triacetin. The pH of this solution was about 6.0.

Solution N was slowly added to about 100 ml of Solution M, with constantstirring. The result was a mobile, white emulsion having a pH of about8.2. It was observed that, upon standing, the resulting solution tendedto separate, but the emulsion could be maintained with some agitation.Final concentrations of starting components, by weight, in this solutionwere as follows (the remaining constituent being water):

About 2.5% peanut oil;

About 2.5% Myvacet 9-45;

About 0.25% Witconol H31A;

About 0.1% Carbopol 934-P;

About 0.5% triacetin; and

About 0.25% diethanolamine.

The above emulsion was tested as follows:

A small hay bale having dimensions of about 4"×15"×20" was sprayed withabout 50 to 75 ml of the above solution, with some spreading to ensurecomplete coverage of the bale. The bale was allowed to dry.

The bale was exposed to water by spraying with a hose for about 1.5hours, to approximate about a 1.5 inch rainfall. The bale was thenallowed to dry.

The dried bale was observed to have its individual fibers substantiallycoated with a slightly brownish somewhat oily coating. The outer hayparticles were observed to be particularly well coated and showedsubstantial evidence of water repellency. Very little adhesion among thehay fibers was observed.

GENERAL OBSERVATIONS WITH RESPECT TO FORMULATION 1, 2, 3 AND 4COMPOSITIONS

In general, all four formulations provide good coatings for harvestedmaterial such as hay. The coated feed stock appears to be acceptable toanimals, and the preferred coatings can be manufactured from materialsreadily available. It is noted that, for the most part, the coatingswill only be found in the outer 7% to 25% of the hay being treated, sothat the amount of composition eaten by any animal would be relativelylow.

The coatings, again, are particularly useful for imparting to the hay orother material coated a moisture resistant or repellent. This isachieved with either the emulsion coating or the adhesive coating.Further, both coatings may include antimicrobial compounds therein, toaid in preservation of the material coated. However, both the emulsioncoatings and the adhesive coatings are effective in the absence of theantimicrobial compounds or preserving agents. Formulation 1, 2 and 3compounds also include substances leading to an adhesive effect, thusaiding in the preservation of the physical integrity of the materialcoated. This can be particularly important in very large hay bales orhaystacks, or where it is anticipated that the hay will be exposed tosevere weather elements or rough travel. However it will be understoodthat this invention may be applied to agricultural products other thanhay.

It is to be understood that while certain embodiments of the presentinvention have been illustrated and described, it is not to be limitedto the specific forms described, except as limited by the followingclaims.

What is claimed and desired to be secured by Letters Patent is asfollows:
 1. A composition for spreading over outer portions of cutagricultural products, such as hay, to generate a moisture resistantadhesive coating thereover; said composition including:(a) at least oneadhesive-forming constituent; (b) at least one emulsifying agent; (c) atleast one plasticizer agent; (d) said adhesive forming constituent beingsodium caseinate; (e) and including sodium carboxymethylcellulose, apolyethelene glycol 400 emulsifier and glyceryl triacetate.
 2. Acomposition according to claim 1 including:(a) at least oneantimicrobial-acting preserving agent.
 3. A composition according toclaim 1 wherein:(a) said adhesive-forming constituent is formed fromcasein.
 4. A composition according to claim 1 including:(a) propionicacid.
 5. An adhesive forming mucilage for spreading upon cutagricultural products such as hay to form an adhesive water-resistantcoating thereon, with substantial antimicrobial activity; saidcomposition have an aqueous base including the following components, inthe following ratios by weight:(a) about 5 parts to 10 parts casein; (b)about 0.5 to about 1.0 parts diethanolamine; (c) about 0.25 to about 0.5parts sodium carboxymethylcellulose; (d) about 0.25 to about 0.5 partsglyceryl triacetate; (e) about 0.5 to about 1.5 parts polyethyleneglycol 400 emulsifier; and (f) about 0.1 to about 0.4 parts propionicacid.
 6. A water based adhesive mucilage for use in coating cutagricultural products such as hay to form an outer, water-resistant,adhesive layer thereon having substantial antimicrobial activity; saidcomposition including the following, by weight:(a) about 5 to about 10%casein; (b) about 0.5 to about 1.0% diethanolamine; (c) about 0.25 toabout 0.5% sodium carboxymethylcellulose; (d) about 0.25 to about 0.5%glyceryl triacetate; (e) about 0.5 to about 1.5% of a polyethyleneglycol 400 emulsifier; and (f) about 0.1 to about 0.4% propionicacid;(i) the remainder of the composition substantially comprisingwater.
 7. A water based adhesive mucilage for use in applying to cutagricultural products such as hay to form an outer adhesive,water-resistant, substantially microbial acting, layer thereon; saidmucilage being formed from the following components, in the followingratios, by weight:(a) about 6 parts to about 10 parts casein; (b) about0.5 parts to about 1.2 parts diethanolamine; (c) about 0.05 parts toabout 0.2 parts of a polyacrylamide emulsifying agent; and (d) about 0.2parts to about 0.4 parts propionic acid.
 8. A water based adhesivemucilage for application to harvested materials such as hay to form anouter adhesive, water-resistant, substantially antimicrobial-acting,coating thereon; said adhesive mucilage including the following, byweight:(a) about 6 to about 10% casein; (b) about 0 5 to about 1.2%diethanolamine; (c) about 0.05 to about 0.2% of a polyacrylamideemulsifying agent; and (d) about 0.2 to about 0.4% propionic acid;(i)the remainder of the composition substantially comprising water.
 9. Asubstantially dry powder composition suitable for dilution with water toform an adhesive mucilage, the adhesive mucilage being suitable forspreading over cut agricultural products such as hay to form an outeradhesive, generally water-resistant, preservative containing layerthereon; said dry mix including the following, by weight:(a) betweenabout 70 parts and 85 parts casein; (b) between about 16 parts and about20 parts sodium carbonate; (c) between about 1.5 parts and about 3.5parts potassium sorbate; and (d) between about 0.2 and 0.6 parts of apolyacrylamide emulsifying agent.
 10. A preferred dry mix utilizable toform, upon addition of water, an adhesive mucilage; the adhesivemucilage being suitable for spreading upon cut agricultural productssuch as hay to form an outer, adhesive, substantially water-resistantand preservative-containing layer therein; said dry mix including thefollowing constituents, by weight:(a) about 79 parts casein; (b) about18 parts sodium carbonate; (c) about 2.6 parts potassium sorbate; and(d) about 0.4 parts of a polyacrylamide emulsifying agent.
 11. A methodof preparing an adhesive mucilage for use in treating hay or otheragricultural material; said method comprising the steps of:(a) mixingcasein with water and a base to form a first mixture; (b) adding anemulsion-forming effective amount of a polyacrylamide emulsifying agentto said first mixture; and (c) adding an antimicrobial-effectivepreserving agent to the mixture resulting from step (b).
 12. A method ofpreparing a dry mix composition suitable for application, upon dilutionwith water, to hay or other cut agricultural products for preservingsame and generating adhesiveness therein; said method comprising thestep of:(a) mixing casein, sodium carbonate, a polyacrylamide polymericemulsifier, and a solid preserving agent together to form said dry mix.13. A powder mix substantially soluble in water, in which it forms anadhesive mucilage which can be applied to harvested materials such ashay, milo, or silage, consisting essentially of:(a) casein; (b) at leastone emulsifying agent; (c) at least one preserving agent; and (d) sodiumcarbonate.